(19)

*EP003351506B1*
(11) EP 3 351 506 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C01F 11/46 (2006.01) C01B 25/22 (2006.01)
30.09.2020 Bulletin 2020/40 C01B 25/229 (2006.01)

(21) Application number: 16845634.1 (86) International application number:

PCT/CN2016/096941
(22) Date of filing: 26.08.2016
(87) International publication number:
WO 2017/045520 (23.03.2017 Gazette 2017/12)

(54) METHOD FOR PRODUCING PHOSPHORIC ACID AND BY-PRODUCING ALPHA-HEMIHYDRATE

GYPSUM BY WET-PROCESS
VERFAHREN ZUR HERSTELLUNG VON PHOSPHORSÄURE UND ALPHA-HALBHYDRATGIPS
ALS NEBENPRODUKT DURCH NASSVERFAHREN
PROCÉDÉ DE PRODUCTION D’ACIDE PHOSPHORIQUE ET DE PRODUCTION INTERMÉDIAIRE
D’ALPHA-GYPSE SEMI-HYDRATÉ PAR TRAITEMENT PAR VOIE HUMIDE

(84) Designated Contracting States: • YAO, Hualong

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Linyi
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Shandong 276700 (CN)
PL PT RO RS SE SI SK SM TR • LIU, Yongxiu
Linyi
(30) Priority: 18.09.2015 CN 201510595367 Shandong 276700 (CN)
• LI, Chengzhi
(43) Date of publication of application: Linyi
25.07.2018 Bulletin 2018/30 Shandong 276700 (CN)
• ZHANG, Xixing
(73) Proprietors: Linyi
• Kingenta Ecological Engineering Group Co., Ltd. Shandong 276700 (CN)
Linyi, Shandong 276700 (CN)
• Kingenta Norsterra Chemical Co., Ltd. (74) Representative: Epping - Hermann - Fischer
Guizhou 550400 (CN) Patentanwaltsgesellschaft mbH
Schloßschmidstraße 5
(72) Inventors: 80639 München (DE)
• HU, Zhaoping
Linyi (56) References cited:
Shandong 276700 (CN) CN-A- 102 303 852 CN-A- 103 086 335
• CHEN, Hongkun CN-A- 103 086 335 CN-A- 104 355 560
Linyi CN-A- 105 253 867 US-A- 3 935 298
Shandong 276700 (CN) US-A- 4 501 724
EP 3 351 506 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 3 351 506 B1

Description

[0001] This application claims priority to Chinese Patent Application No. 201510595367.7, entitled "METHOD FOR
PRODUCING PHOSPHORIC ACID AND BY-PRODUCING ALPHA-HEMIHYDRATE GYPSUM BY WET-PROCESS",
5 filed with the State Intellectual Property Office of China on September 18, 2015.

FIELD

[0002] The present invention belongs to the technical field of a method for producing wet-process phosphoric acid, in
10 particular, relates to a method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemi-
hydrate gypsum as by-product.

BACKGROUND

15 [0003] In general, a so-called "wet-process phosphoric acid" actually refers to wet-process phosphoric acid produced
by a sulfuric acid process, that is, phosphoric acid is produced by decomposing a phosphate rock with sulfuric acid. In
China, 80% or more of phosphoric acid is produced by a dihydrate process for wet-process phosphoric acid. The dihydrate
process is characterized in that the process is simple, the technique is mature and the adaptability to rock types is high,
which is especially suitable for low and medium grade rocks and dominates in the wet-process phosphoric acid production.
20 However, there are still some insurmountable deficiencies in the dihydrate process. The application of by-product phos-
phogypsum is subjected to many limitations due to its high phosphorus content, of which only a small part is used to
produce low-grade and low-quality gypsum building materials and cement retarders. Most of phosphogypsum is discarded
or stockpiled, causing serious pollution and waste. Therefore, it is necessary to further improve the conventional wet-
process phosphoric acid production so as to reduce the phosphorous content in phosphogypsum, thereby converting it
25 into a product with high use value.
[0004] Chinese Patent (Publication No. CN103626143A) discloses a method for producing phosphoric acid and by-
producing white gypsum by a wet process. Firstly, phosphate rock powder (pulp) reacts with phosphoric acid at 45 to
70°C under stirring to generate a mixed pulp containing solid impurities. The mixed pulp is subjected to continuous or
discontinuous precipitation and separation to give a mixed solution of phosphoric acid and calcium phosphate, as well
30 as a thick pulp containing solid impurities. Under condition of stirring, sulfuric acid is added to the mixed solution of
phosphoric acid and calcium phosphate and reaction undergoes. The resulting mixture is precipitated, layered and
separated into phosphoric acid and white gypsum. By this method, phosphoric acid and white gypsum are obtained
without the generation of phosphogypsum, eliminating the pollution from the piled phosphogypsum to air, soil and
underground water. In addition, the by-product dihydrate white gypsum has high purity and high whiteness value. How-
35 ever, there are still acid-insoluble residues generated by this method, which is difficult to deal with. In addition, the
dihydrate white gypsum needs to be subjected to dehydrate process or crystal modification process to obtain beta-
gypsum or alpha-gypsum products with high added value.
[0005] Chinese patent (Publication No. CN102001636A) discloses a method for preparing phosphoric acid with a
wide-range concentration and clean gypsum through wet-process from low or medium grade phosphate rock. The
40 method provides a new method for preparing wet-process phosphoric acid - hemi-dihydrate method, of which the by-
product is high quality construction hemihydrate gypsum or functional dihydrate gypsum, making full use of low or medium
grade phosphate rock. However, the method still discharges solid residues and dihydrate gypsum at a similar amount
of the clean gypsum, which is hard to be used.
[0006] Chinese Patent (Publication No. CN1421385) discloses a method for preparing hemihydrate-dihydrate phos-
45 phoric acid. In the method, the precipitation ratio of calcium in reaction tank is controlled and sulfuric acid is added at
two steps. One part of sulfuric acid is added to acid-mixing tank, mixed with diluted phosphoric acid and then added to
the second reaction tank; the other part of sulfuric acid is added to diluted phosphoric acid tank. Alpha-hemihydrate
gypsum is prepared firstly and then transformed to dihydrate gypsum. By-product of the method is still dihydrate gypsum,
which is hard to be used directly. Chinese Patent (Publication No. CN103086335A) discloses a dihydrate-hemihydrate
50 method for producing wet-process phosphoric acid and coproducing by-product alpha-hemihydrate gypsum. ω(P2O5)
concentration of the wet-process phosphoric acid produced by dihydrate-process is from 35% to 39% , and ω(P2O5)
concentration of the wet-process phosphoric acid produced by hemihydrate-process is from 10% to 15% used as an
acid supplemental production of dihydrate process. The by-product, hemihydrate phosphogypsum, contains 5% to 7%
crystal water, in which the mass percentage of free P2O5 is less than 0.4%, and the crystal form of which is alpha-
55 hemihydrate phosphogypsum. In the method, the condition for dihydrate-hemihydrate crystal transformation is not strictly
controlled, and no crystal transformation agent is used to control the aspect ratio of alpha-hemihydrate gypsum. Although
alpha-hemihydrate gypsum product is produced, the strength of alpha-hemihydrate gypsum product is low, so the use
of the product is limited. In addition, phosphorus content of the product is still relative high.

2
 EP 3 351 506 B1

[0007] In summary, the problems in the prior art are: 1) wastes such as acid insoluble substances still need to be
discharged; 2) the coproduced gypsum is a dihydrate, which needs subsequent process to become products with a high
added value, such as alpha-hemihydrate gypsum, beta-hemihydrate gypsum, etc.; 3) the resulting alpha-hemihydrate
gypsum product has low strength and high phosphorus content, limiting its high-end applications.
5 [0008] US 4501724 A discloses a process for the wet process manufacture of concentrated phosphoric acid comprising
the steps of reacting the phosphate rock with an effective amount of acid reagent for yielding phosphoric acid wherein
said reagent is comprised of a mixture of sulfuric acid and gaseous sulfur trioxide, the gaseous sulfur trioxide being
added in an effective amount so as to cause the evaporation of excess water in the feed streams by the release of heat
from the reaction between the sulfur trioxide gas and the rock.
10 [0009] US 3935298 A discloses a process for the preparation of phosphoric acid which comprises mixing phosphate
rock and sulfuric acid in the presence of water, drying the mixture to obtain a solid reaction product between phosphate
rock and sulfuric acid and extracting phosphoric acid from said solid reaction product, said process being characterized
in that phosphate rock and sulfuric acid are mixed under such conditions that the gypsum dihydrate is stably formed
and sulfuric acid is added to the phosphate rock in an amount not exceeding the amount equivalent to the calcium
15 component in the phosphate rock.
[0010] CN 103086335 A discloses a method for the production of phosphoric acid and the combined production of a-
hemihydrate gypsum through a dehydrate-hemihydrate wet phosphoric acid technology.

SUMMARY
20
[0011] The present disclosure aims to overcome the deficiencies of the prior art by providing a method for producing
wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum as by-product. Based on the
traditional wet-process phosphoric acid production, the method can eliminate the discharge of phosphogypsum and acid
insoluble substances, reduce the phosphorus content in gypsum, increase the availability of phosphorus, and produce
25 an alpha-hemihydrate gypsum product which can be directly applied to the building materials industry, through techno-
logical innovations.
[0012] The present disclosure provides the following technical solutions.
[0013] A method for producing alpha-hemihydrate gypsum, comprising the following steps:

30 S1) mixing phosphate rock powder with diluted sulfuric acid and performing an extraction reaction to obtain a mixed
slurry A;

S2) taking a fraction X volume of the mixed slurry A obtained in step S1) and performing a solid and liquid separation
to obtain a supernatant B and a solid C, wherein 0<X<2/3;
35
S3) mixing the solid C and the rest mixed slurry with diluted sulfuric acid; adding a crystal transformation agent;
performing a crystal transformation reaction under heating to obtain a mixed slurry D;

S4) filtering the mixed slurry D obtained in step S3) to obtain an alpha-hemihydrate gypsum.
40
[0014] Preferably, in step S1), the solid-liquid mass ratio of the phosphate rock powder and the diluted sulfuric acid
is from 1:2 to 1:10.
[0015] Preferably, in step S1), the temperature of the extraction reaction is from 30 to 95°C and the duration of the
extraction reaction is from 15 to 60 minutes.
45 [0016] Preferably, the crystal transformation agent is one selected from water-soluble phosphate, water-soluble sulfate,
water-soluble nitrate, water-soluble citrate, water-soluble alkylbenzenesulfonate, water-soluble alkyl fatty acid salt and
water-soluble organic carboxylate, or a combination thereof; the water-soluble phosphate, water-soluble sulfate, water-
soluble nitrate, water-soluble citrate, water-soluble alkylbenzenesulfonate, water-soluble alkyl fatty acid salt and water-
soluble organic carboxylate each independently contain one or more ions of Al3+, Fe3+, Mg2+, K+, Na+ and NH4+.
50 [0017] Preferably, in step S3), the temperature of the crystal transformation reaction is from 60 to 130°C and the
duration of the crystal transformation reaction is from 1.5 to 7.5 hours.
[0018] Preferably, in step S3), the solid-liquid mass ratio of the mixture which is obtained by mixing solid C and the
rest mixed slurry with the diluted sulfuric acid is from 2:1 to 6:1.
[0019] Preferably, in step S3), in the liquid phase resulting from mixing the solid C and the rest mixed slurry with diluted
55 sulfuric acid, the mass fraction of phosphoric acid in terms of P2O5 is from 16% to 25%, and the mass fraction of sulfuric
acid in terms of H2SO4 is from 8% to 12%.
[0020] Preferably, a method for producing alpha-hemihydrate gypsum, comprises the following steps:

3
 EP 3 351 506 B1

(1) adding phosphate rock powder and diluted sulfuric acid in a solid-liquid mass ratio of 1:2 to 1:10 into an extraction
tank; performing extraction reaction for 15 to 60 minutes under controlling the temperature of the extraction tank at
30 to 95°C to obtain a mixed slurry A;

5 (2) taking a fraction X volume of the mixed slurry A obtained in step S1) and performing a solid and liquid separation
to obtain a supernatant B and a solid C; transferring the supernatant B to an acid storage as final phosphoric acid
and transferring the solid C to a crystal transformation tank together with the rest mixed slurry, wherein 0<X<2/3;

(3) adding diluted sulfuric acid to the crystal transformation tank; controlling the liquid-solid ratio as well as the
10 content of P2O5 and H2SO4 in the liquid phase of phosphoric acid after decalcification to obtain a mixed slurry;
adding a crystal transformation agent and performing a crystal transformation reaction for 1.5 to 7.5 hours to obtain
a mixed acid slurry D, wherein the temperature of the crystal transformation tank is maintained at 60 to 130°C;

(4) separating solid and liquid in the mixed acid slurry D obtained in step (3) to obtain a solid E and a filtrate F;
15 washing the solid E with hot water to obtain a washing liquid H and a solid G; and drying the solid G to obtain an
alpha-hemihydrate gypsum;

(5) introducing the filtrate F in step (4) into the extraction tank of step (1) to continue the extraction of phosphate
rock powder; introducing the washing liquid H into a sulfuric acid diluting tank to dilute concentrated sulfuric acid,
20 which is used for the extraction process of step (1) and the crystal transformation reaction of step (3).

[0021] In the present disclosure, the whole system becomes a circulation system through step (2). The phosphoric
acid generated in the step (1) is excessive in the subsequent crystal transformation process, and through step (2), not
only a part of product phosphoric acid is obtained, but also a smooth phosphorus cycle in the whole system is ensured.
25 [0022] According to the present disclosure, it is preferred that the fineness of the phosphate rock powder in step (1)
is from 80 to 100 meshes and the phosphorus pentoxide content in the phosphate rock powder is from 10 to 40% by
mass fraction.
[0023] According to the present disclosure, it is preferred that the mass concentration of diluted sulfuric acid in steps
(1) and (3) is from 20 to 40%, more preferably from 20 to 35%.
30 [0024] According to the present disclosure, it is preferred that the mass fraction of sulfate ions in the mixed slurry A
in step (1) is less than 1%.
[0025] According to the present disclosure, it is preferred that in step (3), the liquid-solid mass ratio of the mixed acid
solution after decalcification and the rest slurry is from 2:1 to 6:1, that is, the liquid-solid mass ratio of mixtures of the
solid C, the rest mixed slurry and the added diluted sulfuric acid is from 2:1 to 6:1; wherein the liquid phosphoric acid in
35 terms of P2O5 accounts for 16% to 25% by mass fraction of the mixed acid, and the sulfuric acid in terms of H2SO4
accounts for 8% to 12% by mass fraction of the mixed acid. More preferably, in step (3), the liquid-solid mass ratio of
the mixed acid solution after decalcification and the rest slurry is from 3:1 to 5:1, wherein the liquid phosphoric acid in
terms of P2O5 accounts for 18% to 23% by mass fraction of the mixed acid, and the sulfuric acid in terms of H2SO4
accounts for 9% to 10% by mass fraction of the mixed acid.
40 [0026] According to the present disclosure, it is preferred that the crystal transformation agent in step (3) is one selected
from a water-soluble phosphate, water-soluble sulfate, water-soluble nitrate, water-soluble citrate, water-soluble alkyl-
benzenesulfonate, water-soluble alkyl fatty acid salt and water-soluble organic carboxylate, or a combination thereof,
which contains Al3+, Fe3+, Mg2+, K+, Na+, NH4+ ions.
[0027] More preferably, the crystal transformation agent added in step (3) is a combination of sodium citrate, ferric
45 sulfate and sodium lignosulfonate; or a combination of sodium nitrate, magnesium sulfate and sodium dodecyl sulfonate;
or a combination of sodium phosphate, aluminum sulfate and sodium lignosulfonate; or a combination of ammonium
nitrate, magnesium sulfate and sodium chloride.
[0028] Even more preferably, the combination of the crystal transformation agent is one of the following combinations
by mass ratio:
50
a. sodium citrate : ferric sulfate : sodium lignosulfonate = 1.00 : 1.50∼2.00 : 0.30∼0.90;

b. sodium nitrate : magnesium sulfate : sodium dodecyl sulfonate = 1.00 : 1.50∼2.00 : 0.30∼0.90;

55 c. sodium phosphate : aluminum sulfate : sodium lignosulfonate = 1.00 : 1.50∼2.00 : 0.40∼0.90;

d. ammonium nitrate : magnesium sulfate : sodium chloride = 1.00 :1.60∼2.20 : 0.50∼0.80.

4
 EP 3 351 506 B1

[0029] According to the present disclosure, it is preferred that the total amount of the crystal transformation agent
added in step (3) is from 0.1% to 1.0% by mass of the mixed slurry.
[0030] According to the present disclosure, it is preferred that the temperature of the hot water in step (4) is from 80
to 90°C.
5 [0031] According to the present disclosure, it is preferred that the drying temperature in step (4) is from 110 to 180°C,
more preferably from 110 to 130°C.
[0032] According to the present disclosure, it is preferred that vapor generated in the dilution process in step (5) is
introduced into the crystal transformation tank in step (3) to provide heat for reaction.
[0033] Even more preferably, a method for producing alpha-hemihydrate gypsum, comprises the following steps:
10
(1) adding phosphate rock powder and diluted sulfuric acid with a mass concentration of 20% into an extraction tank
according to a solid-liquid mass ratio of 1:4, wherein the fineness of the phosphate rock powder is 100-mesh and
the phosphorus pentoxide content in the phosphate rock is 32%; performing an extraction reaction for 30 minutes
wherein controlling the temperature of the extraction tank at 80°C under stirring to obtain a mixed slurry A;
15
(2) taking a fraction of 1/6 volume of the mixed slurry A obtained in step S1) and performing a solid and liquid
separation to obtain a supernatant B and a solid C; transferring the supernatant B to an acid storage as final
phosphoric acid and transferring the solid C to a crystal transformation tank together with the rest mixed slurry;

20 (3) adding diluted sulfuric acid with a mass concentration of 20% to the crystal transformation tank; controlling the
liquid-solid mass ratio of mixed acid solution after decalcification and slag slurry at 6:1 to obtain a mixed slurry,
wherein the liquid phosphoric acid in terms of P2O5 is 20% by mass fraction of the mixed acid and the sulfuric acid
in terms of H2SO4 is 9% by mass fraction of the mixed acid; after obtaining the mixed slurry, adding crystal trans-
formation agents: iron sulfate accounted for 0.23% of the mass of the mixed slurry, sodium citrate accounted for
25 0.12% of the mass of the mixed slurry, and sodium lignosulfonate accounted for 0.08% of the mass of the mixed
slurry; performing crystal transformation reaction for 3h while maintaining the temperature of crystal transformation
tank at 110°C to obtain a mixed acid slurry D;

(4) separating solid and liquid in the mixed acid slurry D obtained in step (3) to obtain a solid E and a filtrate F;
30 washing the solid E with 85°C hot water to obtain a washing liquid H and a solid G; and drying the solid G by a blow-
dryer at a drying temperature of 110°C to obtain an alpha-hemihydrate gypsum;

(5) introducing the filtrate F in step (4) into the extraction tank of step (1) to continue the extraction of phosphate
rock powder; introducing the washing liquid H into a sulfuric acid diluting tank to dilute concentrated sulfuric acid,
35 which is used for the extraction process of step (1) and the crystal transformation process of step (3); introducing
vapor generated during the dilution process into the crystal transformation tank to provide heat for reaction.

[0034] The principle of the present disclosure is that phosphate rock powder is decomposed by a mixed acid of sulfuric
acid and phosphoric acid to transform all the calcium ions in the phosphate rock to dihydrate gypsum, followed by adding
40 a crystal transformation agent and controlling the conditions in the mixed acid solution of sulfuric acid and phosphoric
acid to directly produce alpha-hemihydrate gypsum.
[0035] The present disclosure involves the chemical reaction formulas as follows:

Ca5F(PO4)3 + 7H3PO4 → 5Ca(H2PO4)2 + HF↑

45
Ca(H2PO4)2 + H2SO4 + 2H2O = 2H3PO4 + CaSO4•2H2O

CaSO 4•2H2O → CaSO4•1/2H2O

50 [0036] The crystal transformation conditions in the present disclosure is that, in a mixed acid solution of phosphoric
acid and sulfuric acid, under a certain temperature and crystal transformation agent, the dihydrate gypsum is dissolved
in the strong acid environment and water molecules are discharged during the recombination process; new crystal nuclei
is formed, small crystal nuclei dissolves and large crystal nuclei grows, which is a common characteristic of the same
kind of crystal. Under the strong acid condition, the crystal transformation agent compounded in the present disclosure
55 can promote the crystalline morphology of gypsum to grow toward the desired hexagonal short cylindrical shape. The
resulting crystalline morphology would not change even being washed by a solvent such as ethanol or water, and can
maintain the original morphology in water for a long time, which has completely the same characteristics as alpha-
hemihydrate gypsum generated by hydrothermal method.

5
 EP 3 351 506 B1

[0037] The alpha-hemihydrate gypsum of the present disclosure can be dried and ground into gypsum powder, or can
be directly added with water without drying to produce gypsum products such as gypsum boards, gypsum building blocks
and gypsum members.
[0038] In the present disclosure, the washing liquid is used to dilute the concentrated sulfuric acid, whereby on one
5 hand, the recycling of the washing liquid avoids the generation of liquid wastes; on the other hand, the vapor generated
by the dilution heat of the concentrated sulfuric acid is fully utilized, which is introduced into the crystal transformation
tank for maintaining the temperature and heat required for the crystal transformation reaction, thereby achieving the
recycling of the dilution heat. According to the actual production, a production line, which has an annual production of
10,000 tons of hemihydrate gypsum, will save about 600,000 Yuan by using the dilution heat from concentrated sulfuric
10 acid.
[0039] The present disclosure has the following beneficial effects.

1. Comparing with conventional wet-process phosphoric acid production, the present disclosure can produce an
alpha-hemihydrate gypsum product capable of being directly applied to the building materials industry, realizing the
15 industrial continuous large-scale production and resolving the problem that phosphogypsum resulted from the con-
ventional wet-process phosphoric acid production is difficult to be treated.

2. Phosphogypsum, a by-product of the traditional wet-process phosphoric acid production, has a high phosphorus
content; in contrast, the alpha-hemihydrate gypsum produced in the present disclosure has a reduced phosphorus
20 content below 0.1%, thereby increasing the availability of phosphorus in the phosphate rock.

3. The morphology of the alpha-hemihydrate gypsum prepared in the present disclosure can be controlled, and the
alpha-hemihydrate gypsum having different aspect ratios can be prepared by adjusting the formulation of the crystal
transformation agent, which can apply to different market demands.
25
4. In the present disclosure, full utilization of the vapor generated by the dilution heat of concentrated sulfuric acid
allows the recycling of the dilution heat, saving the production cost and energy, reducing the emission.

5. In the present disclosure, all the components of the phosphate rock powder can be used, and no environmental
30 pollutants such as waste water and waste phosphogypsum are discharged.

6. The extraction process of the present disclosure does not require precipitation and layering, greatly reducing the
time required for the reaction and aging in the extraction tank, and improving production efficiency.

35 BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 is the schematic of technical flow chart of a method for producing wet-process phosphoric acid and
at the same time obtaining alpha-hemihydrate gypsum as by-product.

40 DETAILED DESCRIPTION

[0041] For further understanding of the present disclosure, the preferred embodiments of the present disclosure are
described below with reference to examples. However, it is to be understood that these descriptions are only for further
illustrating the features and advantages of the present disclosure, rather than limiting the claims of the present disclosure.
45 [0042] The chemical reagents used in the examples of the present disclosure are all commercially available, and the
concentration of the reagent and the content of the mineral components are both in mass percentage.

Examples

50 Example 1

[0043] Phosphate rock mining site: Kailin, Guizhou; phosphorus pentoxide content of the phosphate rock: about 32%.
[0044] A method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product, comprising the following steps:
55
(1) phosphate rock powder and diluted sulfuric acid with a mass concentration of 20% were added into an extraction
tank according to a solid-liquid mass ratio of 1:4, wherein the fineness of the phosphate rock powder was 100
meshes and the phosphorus pentoxide content in the phosphate rock was 32%; extraction reaction was performed

6
 EP 3 351 506 B1

for 30 minutes under stirring to obtain a mixed slurry A, wherein the temperature of the extraction tank was controlled
at 80°C;

(2) solid and liquid in 1/6 volume of the mixed slurry A obtained in step (1) were separated by a filter machine to
5 obtain a supernatant B and a solid C; the supernatant B was transferred to an acid storage as final phosphoric acid
and the solid C was transferred to a crystal transformation tank together with the rest mixed slurry;

(3) diluted sulfuric acid with a mass concentration of 20% was added to the crystal transformation tank; the liquid-
solid mass ratio of the mixed acid solution after decalcification and slag slurry was controlled at 6:1 to obtain a mixed
10 slurry, wherein the liquid phosphoric acid in terms of P2O 5 was 20% by mass of the mixed acid and the sulfuric acid
in terms of H2SO4 was 9% by mass of the mixed acid; after obtaining the mixed slurry, crystal transformation agents
were added: iron sulfate accounted for 0.23% of the mass of the mixed slurry, sodium citrate accounted for 0.12%
of the mass of the mixed slurry, and sodium lignosulfonate accounted for 0.08% of the mass of the mixed slurry;
crystal transformation reaction was performed for 3h to obtain a mixed acid slurry D, wherein the temperature of
15 crystal transformation tank was maintained at 110°C;

(4) solid and liquid in the mixed acid slurry D obtained in step (3) were separated to obtain a solid E and a filtrate
F; the solid E was washed with 85°C hot water to obtain a washing liquid H and a solid G; and the solid G was dried
by a blow-dryer at a drying temperature of 110°C to obtain an alpha-hemihydrate gypsum;
20
(5) the filtrate F in step (4) was introduced into the extraction tank of step (1) to continue the extraction of phosphate
rock powder; the washing liquid H was introduced into a sulfuric acid diluting tank to dilute concentrated sulfuric
acid with a mass percentage of 97%, which was used for the extraction process of step (1) and the crystal trans-
formation process of step (3); vapor generated during the dilution process was introduced into the crystal transfor-
25 mation tank to provide heat for reaction.

Detection results:

[0045] Quimociac gravimetric method was used to test the phosphoric acid product and the concentration was 27%wt.
30 The alpha-hemihydrate gypsum product has a P2O5 content of 0.06 wt%. The alpha-hemihydrate gypsum product
conformed to the industry standard JC/T 2038-2010. Under optical microscope of 200 3 magnification, the alpha-
hemihydrate gypsum showed a short hexagonal cylindrical shape, with an aspect ratio of 1 to 2. The alpha-hemihydrate
gypsum has a 2h bending strength of 9.5MPa, a dry bending strength of 17MPa, a dry compressive strength of 95MPa,
an initial setting time of 8min and a final setting time of 17min.
35
Example 2

[0046] Phosphate rock mining site: Lufa, Guizhou; phosphorus pentoxide content of the phosphate rock: 27%.
[0047] A method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
40 as by-product, comprising the following steps:

(1) phosphate rock powder and diluted sulfuric acid with a mass concentration of 30% were added into an extraction
tank according to a solid-liquid mass ratio of 1:3, wherein the fineness of the phosphate rock powder was 100
meshes and the phosphorus pentoxide content in the phosphate rock was 27%; extraction reaction was performed
45 for 50 minutes under stirring to obtain a mixed slurry A, wherein the temperature of the extraction tank was controlled
at 70°C;

(2) solid and liquid in 2/3 volume of the mixed slurry A obtained in step (1) were separated by a filter machine to
obtain a supernatant B and a solid C; the supernatant B was transferred to an acid storage as final phosphoric acid
50 and the solid C was transferred to a crystal transformation tank together with the rest mixed slurry;

(3) diluted sulfuric acid with a mass concentration of 30% was added to the crystal transformation tank; the liquid-
solid mass ratio of the mixed acid solution after decalcification and slag slurry was controlled at 5:1 to obtain a mixed
slurry, wherein the liquid phosphoric acid in terms of P2O 5 was 20% by mass of the mixed acid and the sulfuric acid
55 in terms of H2SO4 was 12% by mass of the mixed acid; after obtaining the mixed slurry, crystal transformation agents
were added: aluminum sulfate accounted for 0.25% of the mass of the mixed slurry, sodium citrate accounted for
0.09% of the mass of the mixed slurry, and sodium lignosulfonate accounted for 0.06% of the mass of the mixed
slurry; crystal transformation reaction was performed for 2h to obtain a mixed acid slurry D, wherein the temperature

7
 EP 3 351 506 B1

of crystal transformation tank was maintained at 100°C;

(4) solid and liquid in the mixed acid slurry D obtained in step (3) were separated to obtain a solid E and a filtrate
F; the solid E was washed with 90°C hot water to obtain a washing liquid H and a solid G; and the solid G was dried
5 by a blow-dryer at a drying temperature of 110°C to obtain an alpha-hemihydrate gypsum;

(5) the filtrate F in step (4) was introduced into the extraction tank of step (1) to continue the extraction of phosphate
rock powder; the washing liquid H was introduced into a sulfuric acid diluting tank to dilute concentrated sulfuric
acid, which was used for the extraction process of step (1) and the crystal transformation process of step (3); vapor
10 generated during the dilution process was introduced into the crystal transformation tank to provide heat for reaction.

Detection results:

[0048] Quimociac gravimetric method was used to test the phosphoric acid product and the concentration was 22%wt.
15 The alpha-hemihydrate gypsum product has a P2O5 content of 0.08wt%. The alpha-hemihydrate gypsum product con-
formed to the industry standard JC/T 2038-2010. Under optical microscope of 200 3 magnification, the alpha-hemihydrate
gypsum showed a short hexagonal cylindrical shape, with an aspect ratio of 2 to 3. The alpha-hemihydrate gypsum has
a 2h bending strength of 8.0MPa, a dry bending strength of 15MPa, a dry compressive strength of 75MPa, an initial
setting time of 9min and a final setting time of 18min.
20
Example 3

[0049] A method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product was carried out in the same manner as described in Example 1, except that the components and contents
25 of the crystal transformation agent used were different, as shown in Table 1:

Table 1. Components and contents of crystal transformation agent, as well as performances of the resulting product
Combination of
Components and contents
crystal Performances of alpha-hemihydrate gypsum product
30 (wt%)
transformation agent
Exhibiting a short hexagonal cylindrical shape with an aspect
sodium nitrate 0.10 ratio of 1 to 2 under an optical microscope at 200 X
magnesium sulfate 0.20 magnification; a 2h bending strength of 8.0MPa, a dry
1
35 sodium dodecyl bending strength of 16MPa, a dry compressive strength of
benzenesulfonate 0.07 89MPa, an initial setting time of 8min and a final setting time
of 17min.
Exhibiting a short hexagonal cylindrical shape with an aspect
ratio of 2 to 4 under an optical microscope at 200 X
40 ferric sulfate 0.22 sodium
magnification; a 2h bending strength of 7.0MPa, a dry
2 dodecyl benzenesulfonate
bending strength of 14MPa, a dry compressive strength of
0.07
65MPa, an initial setting time of 7min and a final setting time
of 17min.

45 Exhibiting a short hexagonal cylindrical shape with an aspect

ratio of 1 to 2 under an optical microscope at 200 X
sodium phosphate 0.10
magnification; a 2h bending strength of 7.0MPa, a dry
3 aluminum sulfate 0.20
bending strength of 15MPa, a dry compressive strength of
aluminum lignosulfonate 0.07
90MPa, an initial setting time of 6min and a final setting time
50 of 19min.
Exhibiting a short hexagonal cylindrical shape with an aspect
ratio of 3 to 5 under an optical microscope at 200 X
sodium phosphate 0.12 magnification; a 2h bending strength of 7.0MPa, a dry
4
aluminum lignosulfonate 0.14 bending strength of 14MPa, a dry compressive strength of
55 62MPa, an initial setting time of 6min and a final setting time
of 18min.

8
 EP 3 351 506 B1

(continued)

Combination of
Components and contents
crystal Performances of alpha-hemihydrate gypsum product
(wt%)
5 transformation agent
Exhibiting a short hexagonal cylindrical shape with an aspect
ratio of 1 to 2 under an optical microscope at 200 X
ammonium nitrate 0.11
magnification; a 2h bending strength of 8.0MPa, a dry
5 magnesium sulfate 0.21
bending strength of 15MPa, a dry compressive strength of
10 sodium chloride 0.08
93MPa, an initial setting time of 7min and a final setting time
of 19min.
Exhibiting a short hexagonal cylindrical shape with an aspect
ratio of 4 to 5 under an optical microscope at 200 X
15 ammonium sulfate 0.33 magnification; a 2h bending strength of 7.0MPa, a dry
6
sodium citrate 0.18 bending strength of 13MPa, a dry compressive strength of
60MPa, an initial setting time of 8min and a final setting time
of 20min.
Exhibiting a short hexagonal cylindrical shape with an aspect
20
ratio of 7 to 8 under an optical microscope at 200 X
potassium nitrate 0.10 ferric
magnification; a 2h bending strength of 6.0MPa, a dry
7 sulfate 0.21 sodium
bending strength of 10MPa, a dry compressive strength of
acetate0.12
50MPa, an initial setting time of 3min and a final setting time
of 10min.
25
Exhibiting a short hexagonal cylindrical shape with an aspect
ratio of 5 to 7 under an optical microscope at 200 X
potassium nitrate 0.19 sodium magnification; a 2h bending strength of 5.0MPa, a dry
8
acetate0.10 bending strength of 9MPa, a dry compressive strength of
30 45MPa, an initial setting time of 4min and a final setting time
of 13min.

[0050] From the above table, it can be seen that gypsum powder prepared by the present disclosure has an aspect
ratio of < 10 can be obtained, indicating that the morphology of the alpha-hemihydrate gypsum prepared in the present
35 disclosure can be controlled, and the alpha-hemihydrate gypsum having different aspect ratios can be prepared by
adjusting the formulation of the crystal transformation agent, which can apply to different market demands.

Example 4

40 [0051] The amount of vapor (t) generated from per production of 1 ton of alpha-hemihydrate gypsum in the actual
production process of examples 1 to 3 was detected and shown in Table 2.

Table 2. Results of vapor generated by a vapor recycling process from concentrated sulfuric acid diluting tank in
examples 1-3
45
Example 1 Example 2 Example 3 (Combination 1) Average value
0.0436 0.0420 0.0422 0.0426

[0052] As shown in Table 2, by using the vapor recycling process from sulfuric acid diluting tank, 0.0426 ton of vapor
50
in average is produced per production of 1 ton of alpha-hemihydrate gypsum. An alpha-hemihydrate gypsum production
line having an annual output of 100,000 tons can produce a benefit of 639,000 Yuan, as calculated according to the
price of 150 Yuan per ton of vapor.

55
Claims

1. A method for producing alpha-hemihydrate gypsum, comprising the following steps:

9
 EP 3 351 506 B1

S1) mixing phosphate rock powder with diluted sulfuric acid and performing an extraction reaction to obtain a
mixed slurry A;
S2) taking a fraction of X volume of the mixed slurry A obtained in step S1) and performing a solid and liquid
separation to obtain a supernatant B and a solid C, wherein 0<X≤2/3;
5 S3) mixing the solid C and the rest mixed slurry with diluted sulfuric acid; adding a crystal transformation agent;
performing a crystal transformation reaction under heating to obtain a mixed slurry D;
S4) filtering the mixed slurry D obtained in step S3) to obtain an alpha-hemihydrate gypsum.

2. The method for producing alpha-hemihydrate gypsum according to claim 1, wherein in step S1), the solid-liquid
10 mass ratio of the phosphate rock powder to the diluted sulfuric acid is from 1:2 to 1:10.

3. The method for producing alpha-hemihydrate gypsum according to claim 1, wherein in step S1), the temperature
of the extraction reaction is from 30 to 95°C and the duration of the extraction reaction is from 15 to 60 minutes.

15 4. The method for producing alpha-hemihydrate gypsum according to claim 1, wherein the crystal transformation agent
is one selected from water-soluble phosphate, water-soluble sulfate, water-soluble nitrate, water-soluble citrate,
water-soluble alkylbenzenesulfonate, water-soluble alkyl fatty acid salt and water-soluble organic carboxylate, or a
combination thereof; the water-soluble phosphate, water-soluble sulfate, water-soluble nitrate, water-soluble citrate,
water-soluble alkylbenzenesulfonate, water-soluble alkyl fatty acid salt and water-soluble organic carboxylate each
20 independently contain one or more ion(s) of Al3+, Fe3+, Mg2+, K+, Na+ and NH4+.

5. The method for producing alpha-hemihydrate gypsum according to claim 1, wherein in step S3), the temperature
of the crystal transformation reaction is from 60 to 130°C and the duration of the crystal transformation reaction is
from 1.5 to 7.5 hours.
25
6. The method for producing alpha-hemihydrate gypsum according to claim 1, wherein in step S3), the solid-liquid
mass ratio of a mixture of solid C and the rest mixed slurry to the diluted sulfuric acid is from 2:1 to 6:1.

7. The method for producing alpha-hemihydrate gypsum according to claim 1, wherein in step S3), in the liquid phase
30 resulting from mixing the solid C and the rest mixed slurry with diluted sulfuric acid, the mass fraction of phosphoric
acid in terms of P2O5 is from 16% to 25%, and the mass fraction of sulfuric acid in terms of H2SO4 is from 8% to 12%.

8. A method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product, comprising the following steps:
35
(1) adding phosphate rock powder and diluted sulfuric acid in a solid-liquid mass ratio of 1:2 to 1:10 into an
extraction tank; performing extraction reaction for 15 to 60 minutes under controlling the temperature of the
extraction tank at 30 to 95°C to obtain a mixed slurry A;
(2) taking a fraction of X volume of the mixed slurry A obtained in step S1) and performing a solid and liquid
40 separation to obtain a supernatant B and a solid C; transferring the supernatant B to an acid storage as final
phosphoric acid and transferring the solid C to a crystal transformation tank together with the rest mixed slurry,
wherein 0<X≤2/3;
(3) adding diluted sulfuric acid to the crystal transformation tank; controlling the liquid-solid ratio as well as the
content of P2O5 and H2SO4 in the liquid phase of phosphoric acid after decalcification to obtain a mixed slurry;
45 adding a crystal transformation agent and performing a crystal transformation reaction for 1.5 to 7.5 hours to
obtain a mixed acid slurry D, wherein the temperature of the crystal transformation tank is maintained at 60 to
130°C;
(4) separating solid and liquid in the mixed acid slurry D obtained in step (3) to obtain a solid E and a filtrate F;
washing the solid E with hot water to obtain a washing liquid H and a solid G; and drying the solid G to obtain
50 an alpha-hemihydrate gypsum;
(5) introducing the filtrate F in step (4) into the extraction tank of step (1) to continue the extraction of phosphate
rock powder; introducing the washing liquid H into a sulfuric acid diluting tank to dilute concentrated sulfuric
acid, which is used for the extraction process of step (1) and the crystal transformation reaction of step (3).

55 9. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product according to claim 8, wherein the fineness of the phosphate rock powder in step (1) is from 80 to 100
meshes and the phosphorus pentoxide content in the phosphate rock powder is from 10 to 40% by mass fraction.

10
 EP 3 351 506 B1

10. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product according to claim 8, wherein the mass concentration of diluted sulfuric acid in steps (1) and (3) is
from 20 to 40%, more preferably from 20 to 35%.

5 11. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product according to claim 8, wherein the mass fraction of sulfate ions in the mixed slurry A in step (1) is less
than 1%.

12. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
10 as by-product according to claim 8, wherein in step (3), the liquid-solid mass ratio of the mixed acid solution after
decalcification and the rest slurry is from 2:1 to 6:1, wherein the liquid phosphoric acid in terms of P2O5 accounts
for 16% to 25% by mass fraction of the mixed acid, and the sulfuric acid in terms of H2SO4 accounts for 8% to 12%
by mass fraction of the mixed acid; preferably, in step (3), the liquid-solid mass ratio of the mixed acid solution after
decalcification and the rest slurry is from 3:1 to 5:1, wherein the liquid phosphoric acid in terms of P2O5 accounts
15 for 18% to 23% by mass fraction of the mixed acid, and the sulfuric acid in terms of H2SO4 accounts for 9% to 10%
by mass fraction of the mixed acid.

13. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product according to claim 8, wherein the crystal transformation agent in step (3) is one selected from a water-
20 soluble phosphate, water-soluble sulfate, water-soluble nitrate, water-soluble citrate, water-soluble alkylbenzenesul-
fonate, water-soluble alkyl fatty acid salt and water-soluble organic carboxylate, or a combination thereof, which
contains Al3+, Fe3+, Mg2+, K+, Na+, NH4+ ions.

14. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
25 as by-product according to claim 13, wherein the crystal transformation agent added in step (3) is a combination of
sodium citrate, ferric sulfate and sodium lignosulfonate; or a combination of sodium nitrate, magnesium sulfate and
sodium dodecyl sulfonate; or a combination of sodium phosphate, aluminum sulfate and sodium lignosulfonate; or
a combination of ammonium nitrate, magnesium sulfate and sodium chloride; wherein the total amount of the crystal
transformation agent added in step (3) is from 0.1% to 1.0% by mass of the mixed slurry; wherein the combination
30 of the crystal transformation agent is one of the following combinations by mass ratio:

a. sodium citrate : ferric sulfate : sodium lignosulfonate = 1.00 : 1.50∼2.00 : 0.30∼0.90;

b. sodium nitrate : magnesium sulfate : sodium dodecyl sulfonate = 1.00 : 1.50∼2.00 : 0.30∼0.90;
c. sodium phosphate : aluminum sulfate : sodium lignosulfonate = 1.00 : 1.50∼2.00 : 0.40∼0.90;
35 d. ammonium nitrate : magnesium sulfate : sodium chloride = 1.00 :1.60∼2.20 : 0.50∼0.80.

15. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product according to claim 8, wherein the temperature of the hot water in step (4) is from 80 to 90°C; wherein
the drying temperature in step (4) is from 110 to 180°C, more preferably from 110 to 130°C.
40
16. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product according to claim 8, wherein vapor generated in the dilution process in step (5) is introduced into
the crystal transformation tank in step (3) to provide heat for reaction.

45 17. The method for producing wet-process phosphoric acid and at the same time obtaining alpha-hemihydrate gypsum
as by-product according to claim 8, comprising the following steps:

(1) adding phosphate rock powder and diluted sulfuric acid with a mass concentration of 20% into an extraction
tank according to a solid-liquid mass ratio of 1:4, wherein the fineness of the phosphate rock powder is 100-
50 mesh and the phosphorus pentoxide content in the phosphate rock is 32%; performing an extraction reaction
for 30 minutes under controlling the temperature of the extraction tank at 80°C under stirring to obtain a mixed
slurry A;
(2) taking a fraction of 1/6 volume of the mixed slurry A obtained in step S1) and performing a solid and liquid
separation to obtain a supernatant B and a solid C; transferring the supernatant B to an acid storage as final
55 phosphoric acid and transferring the solid C to a crystal transformation tank together with the rest mixed slurry;
(3) adding diluted sulfuric acid with a mass concentration of 20% to the crystal transformation tank; controlling
the liquid-solid mass ratio of mixed acid solution after decalcification and slag slurry at 6:1 to obtain a mixed
slurry, wherein the liquid phosphoric acid in terms of P2O5 is 20% by mass fraction of the mixed acid and the

11
 EP 3 351 506 B1

sulfuric acid in terms of H 2SO4 is 9% by mass fraction of the mixed acid; then, adding crystal transformation
agents: iron sulfate accounted for 0.23% of the mass of the mixed slurry, sodium citrate accounted for 0.12%
of the mass of the mixed slurry, and sodium lignosulfonate accounted for 0.08% of the mass of the mixed slurry;
performing crystal transformation reaction for 3h under maintaining the temperature of crystal transformation
5 tank is maintained at 110°C to obtain a mixed acid slurry D;
(4) separating solid and liquid in the mixed acid slurry D obtained in step (3) to obtain a solid E and a filtrate F;
washing the solid E with 85°C hot water to obtain a washing liquid H and a solid G; and drying the solid G by
a blow-dryer at a drying temperature of 110°C to obtain an alpha-hemihydrate gypsum;
(5) introducing the filtrate F in step (4) into the extraction tank of step (1) to continue the extraction of phosphate
10 rock powder; introducing the washing liquid H into a sulfuric acid diluting tank to dilute concentrated sulfuric
acid, which is used for the extraction process of step (1) and the crystal transformation process of step (3);
introducing vapor generated during the dilution process into the crystal transformation tank to provide heat for
reaction.

15
Patentansprüche

1. Verfahren zur Herstellung von Alpha-Halbhydratgips, das die folgenden Schritte umfasst:

20 S1) Mischen von Phosphatgesteinspulver mit verdünnter Schwefelsäure und Durchführen einer Extraktionsre-
aktion, um eine gemischte Aufschlämmung A zu erhalten;
S2) Entnehmen einer Fraktion eines Volumens X der in Schritt S1) erhaltenen gemischten Aufschlämmung A
und Durchführen einer Feststoff- und Flüssigkeitstrennung, um einen Überstand B und einen Feststoff C zu
erhalten, wobei 0<X≤2/3;
25 S3) Mischen des Feststoffs C und der restlichen gemischten Aufschlämmung mit verdünnter Schwefelsäure;
Zugeben eines Kristallumwandlungsmittels; Durchführen einer Kristallumwandlungsreaktion unter Erwärmung,
um eine gemischte Aufschlämmung D zu erhalten;
S4) Filtrieren der in Schritt S3) erhaltenen gemischten Aufschlämmung D, um einen Alpha-Halbhydratgips zu
erhalten.
30
2. Verfahren zur Herstellung von Alpha-Halbhydratgips nach Anspruch 1, wobei in Schritt S1) das Feststoff-Flüssig-
keits-Massenverhältnis des Phosphatgesteinspulvers zur verdünnten Schwefelsäure 1:2 bis 1:10 beträgt.

3. Verfahren zur Herstellung von Alpha-Halbhydratgips nach Anspruch 1, wobei in Schritt S1) die Temperatur der
35 Extraktionsreaktion 30 bis 95°C und die Dauer der Extraktionsreaktion 15 bis 60 Minuten beträgt.

4. Verfahren zur Herstellung von Alpha-Halbhydratgips nach Anspruch 1, wobei das Kristallumwandlungsmittel eines
ist, das aus einem wasserlöslichen Phosphat, wasserlöslichen Sulfat, wasserlöslichen Nitrat, wasserlöslichen Citrat,
wasserlöslichen Alkylbenzolsulfonat, wasserlöslichen Salz einer Alkylfettsäure und wasserlöslichen organischen
40 Carboxylat oder einer Kombination davon ausgewählt ist; wobei das wasserlösliche Phosphat, das wasserlösliche
Sulfat, das wasserlösliche Nitrat, das wasserlösliche Citrat, das wasserlösliche Alkylbenzolsulfonat, das wasser-
lösliche Salz einer Alkylfettsäure und das wasserlösliche organische Carboxylat jeweils unabhängig voneinander
ein oder mehrere Ion(en) von Al3+, Fe3+, Mg2+, K+, Na+ und NH4+ enthalten.

45 5. Verfahren zur Herstellung von Alpha-Halbhydratgips nach Anspruch 1, wobei in Schritt S3) die Temperatur der
Kristallumwandlungsreaktion 60 bis 130°C und die Dauer der Kristallumwandlungsreaktion 1,5 bis 7,5 Stunden
beträgt.

6. Verfahren zur Herstellung von Alpha-Halbhydratgips nach Anspruch 1, wobei in Schritt S3) das Feststoff-Flüssig-
50 keits-Massenverhältnis eines Gemischs aus dem Feststoff C und der restlichen gemischten Aufschlämmung zur
verdünnten Schwefelsäure 2:1 bis 6:1 beträgt.

7. Verfahren zur Herstellung von Alpha-Halbhydratgips nach Anspruch 1, wobei in Schritt S3) in der Flüssigphase, die
sich aus dem Vermischen des Feststoffs C und der restlichen gemischten Aufschlämmung mit verdünnter Schwe-
55 felsäure ergibt, der Massenanteil an Phosphorsäure, ausgedrückt als P2O 5, 16% bis 25% beträgt, und der Massen-
anteil an Schwefelsäure, ausgedrückt als H2SO4, 8% bis 12% beträgt.

8. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-

12
 EP 3 351 506 B1

dratgips als Nebenprodukt, das die folgenden Schritte umfasst:

(1) Zugeben von Phosphatgesteinspulver und verdünnter Schwefelsäure in einem Feststoff-Flüssigkeits-Mas-

senverhältnis von 1:2 bis 1:10 in einen Extraktionstank; Durchführen der Extraktionsreaktion für 15 bis 60
5 Minuten unter Steuerung der Temperatur des Extraktionstanks auf 30 bis 95°C, um eine gemischte Aufschläm-
mung A zu erhalten;
(2) Entnehmen einer Fraktion eines Volumens X der in Schritt S1) erhaltenen gemischten Aufschlämmung A
und Durchführen einer Feststoff- und Flüssigkeitstrennung, um einen Überstand B und einen Feststoff C zu
erhalten; Überführen des Überstands B in einen Säurespeicher als Endphosphorsäure und Überführen des
10 Feststoffs C in einen Kristallumwandlungstank zusammen mit der restlichen gemischten Aufschlämmung, wobei
0<X≤2/3;
(3) Zugeben von verdünnter Schwefelsäure in den Kristallumwandlungstank; Steuern des Flüssigkeits-Feststoff-
Verhältnisses sowie des Gehalts an P2O5 und H2SO4 in der Flüssigphase der Phosphorsäure nach einer
Entkalkung, um eine gemischte Aufschlämmung zu erhalten; Zugeben eines Kristallumwandlungsmittels und
15 Durchführen einer Kristallumwandlungsreaktion für 1,5 bis 7,5 Stunden, um eine Mischsäureaufschlämmung
D zu erhalten, wobei die Temperatur des Kristallumwandlungstanks auf 60 bis 130°C gehalten wird;
(4) Trennen von Feststoff und Flüssigkeit in der in Schritt (3) erhaltenen Mischsäureaufschlämmung D, um
einen Feststoff E und ein Filtrat F zu erhalten; Waschen des Feststoffs E mit heißem Wasser, um eine Wasch-
flüssigkeit H und einen Feststoff G zu erhalten; und Trocknen des Feststoffs G, um einen Alpha-Halbhydratgips
20 zu erhalten;
(5) Einleiten des Filtrats F in Schritt (4) in den Extraktionstank von Schritt (1), um die Extraktion von Phosphat-
gesteinspulver fortzusetzen; Einleiten der Waschflüssigkeit H in einen Schwefelsäure-Verdünnungstank, um
konzentrierte Schwefelsäure zu verdünnen, die für den Extraktionsprozess von Schritt (1) und die Kristallum-
wandlungsreaktion von Schritt (3) verwendet wird.
25
9. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
dratgips als Nebenprodukt nach Anspruch 8, wobei die Feinheit des Phosphatgesteinspulvers in Stufe (1) einer
Siebgröße von 80 bis 100 entspricht und der Phosphorpentoxidgehalt im Phosphatgesteinspulver 10 bis 40% des
Massenanteils beträgt.
30
10. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
dratgips als Nebenprodukt nach Anspruch 8, wobei die Massenkonzentration von verdünnter Schwefelsäure in den
Schritten (1) und (3) 20 bis 40%, bevorzugter 20 bis 35% beträgt.

35 11. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
dratgips als Nebenprodukt nach Anspruch 8, wobei der Massenanteil an Sulfat-Ionen in der gemischten Aufschläm-
mung A in Schritt (1) weniger als 1% beträgt.

12. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
40 dratgips als Nebenprodukt nach Anspruch 8, wobei in Schritt (3) das Flüssigkeits-Feststoff-Massenverhältnis zwi-
schen der Mischsäurelösung nach Entkalkung und der restlichen Aufschlämmung 2:1 bis 6:1 beträgt, wobei die
flüssige Phosphorsäure, ausgedrückt als P2O 5, 16% bis 25% des Massenanteils der Mischsäure ausmacht, und
die Schwefelsäure, ausgedrückt als H2SO4, 8% bis 12% des Massenanteils der Mischsäure ausmacht; wobei in
Schritt (3) das Flüssigkeits-Feststoff-Massenverhältnis zwischen der Mischsäurelösung nach Entkalkung und der
45 restlichen Aufschlämmung vorzugsweise 3:1 bis 5:1 beträgt, wobei die flüssige Phosphorsäure, ausgedrückt als
P2O5, einen 18% bis 23% des Massenanteils der Mischsäure ausmacht, und die Schwefelsäure, ausgedrückt als
H2SO4, 9% bis 10% des Massenanteils der Mischsäure ausmacht.

13. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
50 dratgips als Nebenprodukt nach Anspruch 8, wobei das Kristallumwandlungsmittel in Schritt (3) eines ist, das aus-
gewählt ist aus einem wasserlöslichen Phosphat, wasserlöslichen Sulfat, wasserlöslichen Nitrat, wasserlöslichen
Citrat, wasserlöslichen Alkylbenzolsulfonat, wasserlöslichen Salz einer Alkylfettsäure und wasserlöslichen organi-
schen Carboxylat oder einer Kombination davon, das Al3+-, Fe3+-, Mg2+-, K+-, Na+-, NH4+-Ionen enthält.

55 14. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
dratgips als Nebenprodukt nach Anspruch 13, wobei das in Schritt (3) zugesetzte Kristallumwandlungsmittel eine
Kombination aus Natriumcitrat, Eisen(III)-sulfat und Natriumlignosulfonat; oder eine Kombination aus Natriumnitrat,
Magnesiumsulfat und Natriumdodecylsulfonat; oder eine Kombination aus Natriumphosphat, Aluminiumsulfat und

13
 EP 3 351 506 B1

Natriumlignosulfonat; oder eine Kombination aus Ammoniumnitrat, Magnesiumsulfat und Natriumchlorid ist; wobei
die Gesamtmenge des in Schritt (3) zugesetzten Kristallumwandlungsmittels 0,1 Masse-% bis 1,0 Masse-% der
gemischten Aufschlämmung beträgt; wobei es sich bei der Kombination des Kristallumwandlungsmittels um eine
der folgenden Kombinationen, im Massenverhältnis, handelt:
5
a. Natriumcitrat : Eisensulfat : Natriumlignosulfonat = 1,00 : 1,50∼2,00 : 0,30∼0,90;
b. Natriumnitrat : Magnesiumsulfat : Natriumdodecylsulfonat = 1,00 : 1,50∼2,00 : 0,30∼0,90;
c. Natriumphosphat : Aluminiumsulfat : Natriumlignosulfonat = 1,00 : 1,50∼2,00 : 0,40∼0,90;
d. Ammoniumnitrat : Magnesiumsulfat : Natriumchlorid = 1,00 : 1,60∼2,20 : 0,50∼0,80.
10
15. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
dratgips als Nebenprodukt nach Anspruch 8, wobei die Temperatur des heißen Wassers in Schritt (4) 80 bis 90°C
beträgt; wobei die Trocknungstemperatur in Schritt (4) 110 bis 180°C, bevorzugter 110 bis 130°C beträgt.

15 16. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
dratgips als Nebenprodukt nach Anspruch 8, wobei im Verdünnungsprozess in Schritt (5) erzeugter Dampf in Schritt
(3) in den Kristallumwandlungstank eingeleitet wird, um Wärme für die Reaktion bereitzustellen.

17. Verfahren zur Herstellung von Nassprozess-Phosphorsäure und zur gleichzeitigen Gewinnung von Alpha-Halbhy-
20 dratgips als Nebenprodukt nach Anspruch 8, das die folgenden Schritte umfasst:

(1) Zugeben von Phosphatgesteinspulver und verdünnter Schwefelsäure mit einer Massenkonzentration von
20% in einen Extraktionstank gemäß einem Feststoff-Flüssigkeits-Massenverhältnis von 1:4, wobei die Feinheit
des Phosphatgesteinspulvers einer Siebgröße von 100 entspricht und der Phosphorpentoxidgehalt im Phos-
25 phatgestein 32% beträgt; Durchführen einer Extraktionsreaktion für 30 Minuten unter Steuerung der Temperatur
des Extraktionstanks auf 80°C unter Rühren, um eine gemischte Aufschlämmung A zu erhalten;
(2) Entnehmen einer Fraktion von 1/6 des Volumens der in Schritt S1) erhaltenen gemischten Aufschlämmung
A und Durchführen einer Feststoff- und Flüssigkeitstrennung, um einen Überstand B und einen Feststoff C zu
erhalten; Überführen des Überstands B in einen Säurespeicher als Endphosphorsäure und Überführen des
30 Feststoffs C in einen Kristallumwandlungstank zusammen mit der restlichen gemischten Aufschlämmung;
(3) Zugeben von verdünnter Schwefelsäure mit einer Massenkonzentration von 20% in den Kristallumwand-
lungstank; Steuern des Flüssigkeits-Feststoff-Massenverhältnisses zwischen der Mischsäurelösung nach der
Entkalkung und der Schlackenaufschlämmung auf 6:1, um eine gemischte Aufschlämmung zu erhalten, wobei
die flüssige Phosphorsäure, ausgedrückt als P2O5, 20% des Massenanteils der Mischsäure ausmacht, und die
35 Schwefelsäure, ausgedrückt als H2SO4, 9% des Massenanteils der Mischsäure ausmacht; dann Zugeben von
Kristallumwandlungsmitteln: Eisensulfat, das 0,23% der Masse der gemischten Aufschlämmung ausmacht,
Natriumcitrat, das 0,12% der Masse der gemischten Aufschlämmung ausmacht, und Natriumlignosulfonat, das
0,08% der Masse der gemischten Aufschlämmung ausmacht; Durchführen der Kristallumwandlungsreaktion
für 3 Stunden unter Beibehaltung der Temperatur des Kristallumwandlungstanks auf 110°C, um eine Misch-
40 säureaufschlämmung D zu erhalten;
(4) Trennen von Feststoff und Flüssigkeit in der in Schritt (3) erhaltenen Mischsäureaufschlämmung D, um
einen Feststoff E und ein Filtrat F zu erhalten; Waschen des Feststoffs E mit 85°C heißem Wasser, um eine
Waschflüssigkeit H und einen Feststoff G zu erhalten; und Trocknen des Feststoffs G durch einen Gebläse-
trockner bei einer Trocknungstemperatur von 110°C, um einen Alpha-Halbhydratgips zu erhalten;
45 (5) Einleiten des Filtrats F in Schritt (4) in den Extraktionstank von Schritt (1), um die Extraktion des Phosphat-
gesteinspulvers fortzusetzen; Einleiten der Waschflüssigkeit H in einen Schwefelsäure-Verdünnungstank, um
konzentrierte Schwefelsäure zu verdünnen, die für den Extraktionsprozess von Schritt (1) und den Kristallum-
wandlungsprozess von Schritt (3) verwendet wird; Einleiten von Dampf, der während des Verdünnungsprozes-
ses erzeugt wird, in den Kristallumwandlungstank, um Wärme für die Reaktion bereitzustellen.
50

Revendications

1. Procédé de production d’alpha-gypse semi-hydraté, comprenant les étapes suivantes :

55
S1) mélange de poudre de roche de phosphate avec de l’acide sulfurique dilué et exécution d’une réaction
d’extraction pour obtenir une boue mélangée A ;
S2) prélèvement d’une fraction de X volume de la boue mélangée A obtenue à l’étape S1) et exécution d’une

14
 EP 3 351 506 B1

séparation de solide et de liquide pour obtenir un surnageant B et un solide C, sachant que 0<X≤2/3 ;
S3) mélange du solide C et de la boue mélangée restante avec de l’acide sulfurique dilué ; ajout d’un agent de
transformation cristalline ; exécution d’une réaction de transformation cristalline en chauffant pour obtenir une
boue mélangée D ;
5 S4) filtrage de la boue mélangée D obtenue à l’étape S3) pour obtenir un alpha-gypse semi-hydraté.

2. Le procédé de production d’alpha-gypse semi-hydraté selon la revendication 1, sachant qu’à l’étape S1), le rapport
massique solide-liquide de la poudre de roche de phosphate à l’acide sulfurique dilué est de 1:2 à 1:10.

10 3. Le procédé de production d’alpha-gypse semi-hydraté selon la revendication 1, sachant qu’à l’étape S1), la tempé-
rature de la réaction d’extraction est de 30 à 95 °C et la durée de la réaction d’extraction est de 15 à 60 minutes.

4. Le procédé de production d’alpha-gypse semi-hydraté selon la revendication 1, sachant que l’agent de transformation
cristalline est un élément sélectionné parmi un phosphate soluble dans l’eau, un sulfate soluble dans l’eau, un nitrate
15 soluble dans l’eau, un citrate soluble dans l’eau, un alkylbenzènesulfonate soluble dans l’eau, un sel d’acide gras
d’alkyle soluble dans l’eau et un carboxylate organique soluble dans l’eau, ou une combinaison de ceux-ci ; le
phosphate soluble dans l’eau, le sulfate soluble dans l’eau, le nitrate soluble dans l’eau, le citrate soluble dans l’eau,
l’alkylbenzènesulfonate soluble dans l’eau, le sel d’acide gras d’alkyle soluble dans l’eau et le carboxylate organique
soluble dans l’eau contiennent chacun indépendamment un ou plusieurs ions d’Al3+, Fe3+, Mg2+, K+, Na+ et NH4+.
20
5. Le procédé de production d’alpha-gypse semi-hydraté selon la revendication 1, sachant qu’à l’étape S3), la tempé-
rature de la réaction de transformation cristalline est de 60 à 130 °C et la durée de la réaction de transformation
cristalline est de 1,5 à 7,5 heures.

25 6. Le procédé de production d’alpha-gypse semi-hydraté selon la revendication 1, sachant qu’à l’étape S3), le rapport
massique solide-liquide d’un mélange de solide C et de la boue mélangée restante à l’acide sulfurique dilué est de
2:1 à 6:1.

7. Le procédé de production d’alpha-gypse semi-hydraté selon la revendication 1, sachant qu’à l’étape S3), dans la
30 phase liquide résultant du mélange du solide C et de la boue mélangée restante avec de l’acide sulfurique dilué, la
fraction massique d’acide phosphorique en termes de P2O5 est de 16 % à 25 %, et la fraction massique d’acide
sulfurique en termes de H2SO4 est de 8 % à 12 %.

8. Procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
35 gypse semi-hydraté comme produit dérivé, comprenant les étapes suivantes :

(1) ajout de poudre de roche de phosphate et d’acide sulfurique dilué dans un rapport massique solide-liquide
de 1:2 à 1:10 dans une cuve d’extraction ; exécution de la réaction d’extraction pendant 15 à 60 minutes en
commandant la température de la cuve d’extraction à 30 à 95 °C pour obtenir une boue mélangée A ;
40 (2) prélèvement d’une fraction de X volume de la boue mélangée A obtenue à l’étape S1) et exécution d’une
séparation de solide et de liquide pour obtenir un surnageant B et un solide C ; transfert du surnageant B vers
un dispositif de stockage d’acide comme acide phosphorique fini et transfert du solide C vers une cuve de
transformation cristalline conjointement avec la boue mélangée restante, sachant que 0<X≤2/3 ;
(3) ajout d’acide sulfurique dilué à la cuve de transformation cristalline ; commande du rapport liquide-solide
45 ainsi que de la teneur en P2O5 et H2SO 4 dans la phase liquide d’acide phosphorique après décalcification pour
obtenir une boue mélangée ; ajout d’un agent de transformation cristalline et exécution d’une réaction de trans-
formation cristalline pendant 1,5 à 7,5 heures pour obtenir une boue d’acide mélangée D, sachant que la
température de la cuve de transformation cristalline est maintenue à 60 à 130 °C ;
(4) séparation de solide et de liquide dans la boue d’acide mélangée D obtenue à l’étape (3) pour obtenir un
50 solide E et un filtrat F ; lavage du solide E avec de l’eau chaude pour obtenir un liquide de lavage H et un solide
G ; et séchage du solide G pour obtenir un alpha-gypse semi-hydraté ;
(5) introduction du filtrat F à l’étape (4) dans la cuve d’extraction de l’étape (1) pour poursuivre l’extraction de
poudre de roche de phosphate ; introduction du liquide de lavage H dans une cuve de dilution d’acide sulfurique
pour diluer de l’acide sulfurique concentré, qui est utilisé pour le processus d’extraction de l’étape (1) et la
55 réaction de transformation cristalline de l’étape (3).

9. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
gypse semi-hydraté comme produit dérivé selon la revendication 8, sachant que la finesse de la poudre de roche

15
 EP 3 351 506 B1

de phosphate à l’étape (1) est de 80 à 100 mailles et la teneur en pentoxyde de phosphore de la poudre de roche
de phosphate est de 10 à 40 % en fraction massique.

10. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
5 gypse semi-hydraté comme produit dérivé selon la revendication 8, sachant que la concentration massique d’acide
sulfurique dilué aux étapes (1) et (3) est de 20 à 40 %, de manière plus préférentielle de 20 à 35 %.

11. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
gypse semi-hydraté comme produit dérivé selon la revendication 8, sachant que la fraction massique d’ions de
10 sulfate dans la boue mélangée A à l’étape (1) est inférieure à 1 %.

12. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
gypse semi-hydraté comme produit dérivé selon la revendication 8, sachant qu’à l’étape 3, le rapport massique
liquide-solide de la solution d’acide mélangé après décalcification et de la boue restante est de 2:1 à 6:1, sachant
15 que l’acide phosphorique liquide en termes de P2O5 représente 16 % à 25 % en fraction massique de l’acide
mélangé, et l’acide sulfurique en termes de H2SO4 représente 8 % à 12 % en fraction massique de l’acide mélangé ;
de préférence, à l’étape (3), le rapport massique liquide-solide de la solution d’acide mélangé après décalcification
et de la boue restante est de 3:1 à 5:1, sachant que l’acide phosphorique liquide en termes de P2O5 représente 18
% à 23 % en fraction massique de l’acide mélangé, et l’acide sulfurique en termes de H2SO4 représente 9 % à 10
20 % en fraction massique de l’acide mélangé.

13. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
gypse semi-hydraté comme produit dérivé selon la revendication 8, sachant que l’agent de transformation cristalline
à l’étape (3) est un élément sélectionné parmi un phosphate soluble dans l’eau, un sulfate soluble dans l’eau, un
25 nitrate soluble dans l’eau, un citrate soluble dans l’eau, un alkylbenzènesulfonate soluble dans l’eau, un sel d’acide
gras d’alkyle soluble dans l’eau et un carboxylate organique soluble dans l’eau, ou une combinaison de ceux-ci,
qui contient des ions d’Al3+, Fe3+, Mg2+, K+, Na+, et NH4+.

14. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
30 gypse semi-hydraté comme produit dérivé selon la revendication 13, sachant que l’agent de transformation cristalline
ajouté à l’étape (3) est une combinaison de citrate de sodium, de sulfate ferrique et de lignosulfonate de sodium ;
ou une combinaison de nitrate de sodium, de sulfate de magnésium et de sulfonate de dodécyle de sodium ; ou
une combinaison de phosphate de sodium, de sulfate d’aluminium et de lignosulfonate de sodium ; ou une combi-
naison de nitrate d’ammonium, de sulfate de magnésium et de chlorure de sodium ; sachant que la quantité totale
35 de l’agent de transformation cristalline ajouté à l’étape (3) est de 0,1 % à 1,0 % en masse de la boue mélangée ;
sachant que la combinaison de l’agent de transformation cristalline est l’une des combinaisons suivantes en rapport
massique :

a. citrate de sodium : sulfate ferrique : lignosulfonate de sodium = 1,00 : 1,50∼2,00 : 0,30∼0,90 ;

40 b. nitrate de sodium : sulfate de magnésium : sulfonate de dodécyle de sodium = 1,00 : 1,50∼2,00 : 0,30∼0,90 ;
c. phosphate de sodium : sulfate d’aluminium : lignosulfonate de sodium = 1,00 : 1,50∼2,00 : 0,40∼0,90 ;
d. nitrate d’ammonium : sulfate de magnésium : chlorure de sodium = 1,00 : 1,60∼2,20 : 0,50∼0,80.

15. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
45 gypse semi-hydraté comme produit dérivé selon la revendication 8, sachant que la température de l’eau chaude à
l’étape (4) est de 80 à 90 °C ; sachant que la température de séchage à l’étape (4) est de 110 à 180 °C, de manière
plus préférentielle de 110 à 130 °C.

16. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
50 gypse semi-hydraté comme produit dérivé selon la revendication 8, sachant que de la vapeur générée dans le
processus de dilution à l’étape (5) est introduite dans la cuve de transformation cristalline à l’étape (3) pour fournir
de la chaleur pour la réaction.

17. Le procédé de production d’acide phosphorique par traitement par voie humide et d’obtention simultanée d’alpha-
55 gypse semi-hydraté comme produit dérivé selon la revendication 8, comprenant les étapes suivantes :

(1) ajout de poudre de roche de phosphate et d’acide sulfurique dilué avec une concentration massique de 20
% dans une cuve d’extraction selon un rapport massique solide-liquide de 1:4, sachant que la finesse de la

16
 EP 3 351 506 B1

poudre de roche de phosphate est de 100 mailles et la teneur en pentoxyde de phosphore de la roche de
phosphate est de 32 % ; exécution d’une réaction d’extraction pendant 30 minutes en commandant la tempé-
rature de la cuve d’extraction à 80 °C en agitant pour obtenir une boue mélangée A ;
(2) prélèvement d’une fraction de 1/6 de volume de la boue mélangée A obtenue à l’étape S1) et exécution
5 d’une séparation de solide et de liquide pour obtenir un surnageant B et un solide C ; transfert du surnageant
B vers un dispositif de stockage d’acide comme acide phosphorique fini et transfert du solide C vers une cuve
de transformation cristalline conjointement avec la boue mélangée restante ;
(3) ajout d’acide sulfurique dilué avec une concentration massique de 20 % à la cuve de transformation cristalline ;
commande du rapport massique liquide-solide de la solution d’acide mélangé après décalcification et d’une
10 boue de laitier à 6:1 pour obtenir une boue mélangée, sachant que l’acide phosphorique liquide en termes de
P2O5 est de 20 % en fraction massique de l’acide mélangé et l’acide sulfurique en termes de H2SO4 est de 9
% en fraction massique de l’acide mélangé ; ensuite, ajout d’agents de transformation cristalline : sulfate de fer
à raison de 0,23 % de la masse de la boue mélangée, citrate de sodium à raison de 0,12 % de la masse de la
boue mélangée, et lignosulfonate de sodium à raison de 0,08 % de la masse de la boue mélangée ; exécution
15 d’une réaction de transformation cristalline pendant 3 heures en maintenant la température de la cuve de
transformation cristalline à 110 °C pour obtenir une boue d’acide mélangée D ;
(4) séparation de solide et de liquide dans la boue d’acide mélangée D obtenue à l’étape (3) pour obtenir un
solide E et un filtrat F ; lavage du solide E avec de l’eau chaude à 85 °C pour obtenir un liquide de lavage H et
un solide G ; et séchage du solide G par un sécheur à soufflage à une température de séchage de 110 °C pour
20 obtenir un alpha-gypse semi-hydraté ;
(5) introduction du filtrat F à l’étape (4) dans la cuve d’extraction de l’étape (1) pour poursuivre l’extraction de
poudre de roche de phosphate ; introduction du liquide de lavage H dans une cuve de dilution d’acide sulfurique
pour diluer de l’acide sulfurique concentré, qui est utilisé pour le processus d’extraction de l’étape (1) et le
processus de transformation cristalline de l’étape (3) ; introduction de vapeur générée pendant le processus
25 de dilution dans la cuve de transformation cristalline pour fournir de la chaleur pour la réaction.

30

35

40

45

50

55

17
EP 3 351 506 B1

18
 EP 3 351 506 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• CN 201510595367 [0001] • CN 103086335 A [0006] [0010]

• CN 103626143 A [0004] • US 4501724 A [0008]
• CN 102001636 A [0005] • US 3935298 A [0009]
• CN 1421385 [0006]

19